CN110408410A

CN110408410A - Liquid-crystal composition and liquid crystal display element

Info

Publication number: CN110408410A
Application number: CN201910136797.0A
Authority: CN
Inventors: 渡部爱美; 松田尚子; 片野裕子; 远藤浩史; 川上日向子
Original assignee: Chisso Petrochemical Corp
Current assignee: JNC Petrochemical Corp
Priority date: 2018-04-26
Filing date: 2019-02-25
Publication date: 2019-11-05
Also published as: KR20190124631A; JP2019194306A; TW201945525A

Abstract

The present invention provides the vertically oriented liquid-crystal composition and liquid crystal display element that a kind of effect by polymer can reach liquid crystal molecule.The present invention is the nematic liquid-crystal composition for containing polar compound as the first additive and having negative dielectric anisotropy, the composition contains the specific liquid crystal compounds with negative big dielectric anisotropy as first composition, contain the specific liquid crystal compounds with high ceiling temperature or small viscosity as second composition, contain polymerizable compound as the second additive and contain polar compound as third additive, and the present invention is the liquid crystal display element containing the composition.

Description

Liquid-crystal composition and liquid crystal display element

Technical field

The present invention relates to a kind of liquid-crystal composition, liquid crystal display elements containing the composition etc..More particularly to it is a kind of Containing the polar compound (or its polymer) with polymerism base and liquid crystal can be reached by the compound The liquid-crystal composition and liquid crystal display element that the vertically oriented dielectric anisotropy of molecule is negative.

Background technique

In liquid crystal display element, the operating mode based on liquid crystal molecule is classified as phase transformation (phase change, PC), turns round Turn to column (twisted nematic, TN), STN Super TN (super twisted nematic, STN), electrically conerolled birefringence (electrically controlled birefringence, ECB), optical compensation curved (optically Compensated bend, OCB), in-plane switching (in-plane switching, IPS), vertical orientation (vertical Alignment, VA), fringing field switching (fringe field switching, FFS), electric field induction light reaction orientation (field-induced photo-reactive alignment, FPA) isotype.Driving method based on element is classified as Passive matrix (passive matrix, PM) and active matrix (active matrix, AM).PM is classified as static type (static) with multiplexing formula (multiplex) etc., AM be classified as thin film transistor (TFT) (thin film transistor, TFT), metal-insulator-metal type (metal insulator metal, MIM) etc..TFT's is classified as amorphous silicon (amorphous silicon) and polysilicon (polycrystal silicon).The latter is classified as high temperature according to manufacturing step Type and low form.The reflection-type using natural light, the infiltration type using backlight are classified as and using natural light based on light source With the semi-transmission type of both backlights.

Liquid crystal display element contains with nematic liquid-crystal composition.The composition has characteristic appropriate.Pass through The characteristic of the composition is improved, can get the AM element with superperformance.Association in two kinds of characteristics is summarized in following In table 1.The characteristic of composition is further illustrated based on commercially available AM element.Nematic temperature range and element can The temperature range used is associated.Nematic preferred upper limit temperature is about 70 DEG C or more, and nematic preferred lower limit temperature Degree is about -10 DEG C or less.The viscosity of composition and the response time of element are associated.It is excellent in order to show dynamic image with element It is short to be selected as the response time.Preferably it is shorter than 1 millisecond of response time.It is therefore preferable that the viscosity for composition is small.Especially preferably Viscosity under low temperature is small.

The optical anisotropy of composition and the contrast of element are than associated.According to the mode of element, and need big Optical anisotropy or small optical anisotropy, i.e., optical anisotropy appropriate.Optical anisotropy (the Δ n) of composition It is designed to keep contrast ratio maximum with the product (Δ n × d) of the cell gap (d) of element.The value of product appropriate depends on fortune The type of operation mode.In the element of VA mode, the range that described value is about 0.30 μm to about 0.40 μm, IPS mode or FFS mode Element in, range that described value is about 0.20 μm to about 0.30 μm.It is excellent for the element small to cell gap in the case of these It is selected as with big optically anisotropic composition.The big dielectric anisotropy of composition facilitates the electricity of the low threshold in element Pressure, small consumption electric power and big contrast ratio.It is therefore preferable that being big dielectric anisotropy.The big specific resistance of composition Facilitate element big voltage retention and big contrast ratio.It is therefore preferable that be electric with big ratio in the initial stage The composition of resistance.Preferably after prolonged use, with the composition of big specific resistance.Composition to ultraviolet light or heat it is steady It is qualitative associated with the service life of element.When the stability is high, the service life of element is long.Such characteristic is to for monitor lcd For the AM element of device, LCD TV etc. preferably.

In general liquid crystal display element, the vertical orientation of liquid crystal molecule can be reached using specific alignment film of polyimide At.Polymer stabilizing is orientated in the liquid crystal display element of (polymer sustained alignment, PSA) type, makes polymer It is combined with alignment films.Firstly, the composition added with a small amount of polymerizable compound is injected into element.Then, on one side Apply voltage between the substrate of the element, ultraviolet light is irradiated to composition on one side.Polymerizable compound polymerize and The reticular structure of polymer is generated in composition.In the composition, the orientation of liquid crystal molecule can be controlled using polymer, Therefore the response time of element shortens, and the image retention of image is improved.With TN, ECB, OCB, IPS, VA, FFS, FPA etc It can be expected that such effect of polymer in the element of mode.

On the other hand, the liquid crystal containing polymer and polar compound is used in the liquid crystal display element without alignment films Composition.Firstly, the composition added with a small amount of polymerizable compound and a small amount of polar compound is injected into element.This Place, polar compound are adsorbed in the substrate surface of element and are arranged.Liquid crystal molecule is orientated according to the arrangement.Then, Apply voltage between the substrate of the element on one side, ultraviolet light is irradiated to composition on one side.Herein, polymerizable compound carries out Polymerization, and stabilize the orientation of liquid crystal molecule.In the composition, liquid can be controlled using polymer and polar compound The orientation of brilliant molecule, therefore the response time of element shortens, the image retention of image is improved.In turn, without the member of alignment films The step of forming alignment films is not needed in part.Since there is no alignment films, therefore pass through the interaction of alignment films and composition, member The resistance of part will not reduce.In the element of mode with TN, ECB, OCB, IPS, VA, FFS, FPA etc it can be expected that using poly- Close such effect of the combination of object and polar compound.

The composition with positive dielectric anisotropy is used in AM element with TN mode.AM member with VA mode The composition with negative dielectric anisotropy is used in part.Using with just in AM element with IPS mode or FFS mode Or the composition of negative dielectric anisotropy.In the AM element of polymer stabilizing orientating type using have positive or negative dielectric respectively to Anisotropic composition.The composition with positive or negative dielectric anisotropy is used in element without alignment films.With negative The composition of dielectric anisotropy have announcement in patent document 1 below is equal to patent document 5.In the present invention, will have The polar compound (or its polymer) of polymerism base is combined with liquid crystal compounds, and the composition is used to not have and is taken Into the liquid crystal display element of film.

[existing technical literature]

[patent document]

[patent document 1] International Publication 2014-090362

[patent document 2] International Publication 2014-094959

[patent document 3] International Publication 2013-004372

[patent document 4] Japanese Patent Laid-Open 2015-168826 bulletin

[patent document 5] International Publication 2016-015803

Summary of the invention

[problem to be solved by the invention]

Problem of the invention is to provide a kind of liquid crystal containing the polar compound (or its polymer) with polymerism base Composition, herein, polar compound have the high compatibility with liquid crystal compounds at low temperature.Another problem is to provide one Kind can reach the vertically oriented liquid crystal group of liquid crystal molecule by the effect of the polymer generated from the polar compound Close object.Another problem is a kind of liquid-crystal composition, nematic ceiling temperature is high, nematic lower limit temperature is low, viscosity Dielectric anisotropy small, that optical anisotropy is appropriate, negative is big, specific resistance is big, stabilization high to the stability of ultraviolet light, to heat Property big etc the characteristic of high, elastic constant in, meet at least one characteristic.Another problem be provide it is a kind of these characteristics extremely With the liquid-crystal composition of appropriate balance between two kinds few.Another problem is a kind of liquid crystal display member containing such composition Part.Another problem be it is a kind of have the response time is short, voltage retention is big, starting voltage is low, contrast than greatly, the characteristics such as the service life is long AM element.

[technical means to solve problem]

The present invention contains for one kind is selected from least one of the polar compound of polymerism represented by formula (1) compound As the first additive and with the liquid-crystal composition of nematic phase and negative dielectric anisotropy, and contain the composition Liquid crystal display element.

In formula (1),

R¹For hydrogen or the alkyl of carbon number 1 to 15, in the alkyl, at least one-CH₂It can replace through-O- or-S-, at least One-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；Ring A¹And Ring A²It is sub- for 1,2- cyclopropylidene, the Asia 1,3- cyclobutyl, 1,3- cyclopentylene, 1,4- cyclohexylidene, 1,4- cycloheptylidene, 1,4- Cyclohexenyl group, 1,4- phenylene, naphthalene -2,6- diyl, decahydronaphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl, tetrahydro Pyrans -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, in these rings, at least One hydrogen can through fluorine, chlorine, the alkyl of carbon number 1 to 10, the alkenyl of carbon number 2 to 10, carbon number 1 to 10 alkoxy or carbon number 2 to 10 Alkenyloxy group replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；A is 0,1,2,3 or 4；Z¹For singly-bound or carbon number 1 To 6 alkylidene, in the alkylidene, at least one-CH₂It can replace through-O- ,-CO- ,-COO- ,-OCO- or-OCOO-, until A few-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；Sp¹、 Sp²、Sp³And Sp⁴For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least One hydrogen can replace through fluorine or chlorine；Sp⁵For the alkylidene of carbon number 2 to 10, in the alkylidene, at least one-CH₂It can be through-O- Replace；M¹、M²、M³And M⁴The carbon number 1 replaced through fluorine or chlorine for hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least one hydrogen to 5 alkyl；R²For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂CH₂It can be through-CH=CH- or-C ≡ C- Replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；X¹For-OH ,-NH₂、-OR³、-N(R³)₂,-COOH ,-SH or-Si (R³)₃, herein, R³For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, at least one-CH₂It can replace through-O-, at least one A-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine.

[The effect of invention]

Advantages of the present invention is to provide a kind of liquid crystal containing the polar compound (or its polymer) with polymerism base Composition, herein, polar compound have the high compatibility with liquid crystal compounds at low temperature.Another advantage is to provide one Kind can reach the vertically oriented liquid crystal group of liquid crystal molecule by the effect of the polymer generated from the polar compound Close object.Another advantage is a kind of liquid-crystal composition, nematic ceiling temperature is high, nematic lower limit temperature is low, viscosity Dielectric anisotropy small, that optical anisotropy is appropriate, negative is big, specific resistance is big, stabilization high to the stability of ultraviolet light, to heat Property big etc the characteristic of high, elastic constant in, meet at least one characteristic.Another advantage be provide it is a kind of these characteristics extremely With the liquid-crystal composition of appropriate balance between two kinds few.Another advantage is to provide a kind of liquid crystal display containing such composition Element.Another advantage is to provide one kind with the response time is short, voltage retention is big, starting voltage is low, contrast is than big, the service life is long Etc. characteristics AM element.

Specific embodiment

The application method of term in this specification is as described below.Sometimes by " liquid-crystal composition " and " liquid crystal display element " Term be briefly referred to as " composition " and " element "." liquid crystal display element " is liquid crystal display panel and LCD MODULE General name." liquid crystal compounds " are the compounds with the liquid crystalline phase of nematic phase, smectic phase etc, though and without liquid crystalline phase But it is mixed in composition for the purpose for the characteristic for adjusting nematic temperature range, viscosity, dielectric anisotropy etc Compound general name.The compound has the hexatomic ring of such as 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene etc, molecule (liquid crystal molecule) is rodlike (rod like)." polymerizable compound " is added for the purpose for generating polymer in composition is made The compound added.Liquid crystal compounds with alkenyl are in terms of its meaning and are not classified as polymerizable compound.

Liquid-crystal composition is prepared by being mixed plurality of liquid crystals compound.It is regarded in the liquid-crystal composition Need and add the additive of optically active compound or polymerizable compound etc.Even if the case where being added with additive Under, the ratio of liquid crystal compounds is also by the quality percentage (matter of the quality based on the liquid-crystal composition for not including additive Amount %) it indicates.The ratio of additive is by the quality percentage (matter of the quality based on the liquid-crystal composition for not including additive Amount %) it indicates.That is, the ratio of liquid crystal compounds or additive is the gross mass based on liquid crystal compounds and calculates.It is poly- The ratio for closing initiator and polymerization inhibitor is exceptionally to be indicated based on the quality of polymerizable compound.

Sometimes " nematic ceiling temperature " is referred to as " ceiling temperature ".Sometimes referred to as by " nematic lower limit temperature " For " lower limit temperature ".When being expressed in the composition that dielectric anisotropy is positive of " improving dielectric anisotropy ", is referring to its value just Increase to ground, in the composition that dielectric anisotropy is negative, refers to that its value negatively increases." voltage retention is big " refers to member Part in the initial stage not only at room temperature, but also close to ceiling temperature at a temperature of also there is big voltage retention, Moreover, after prolonged use not only at room temperature, and close to ceiling temperature at a temperature of also protected with big voltage Holdup.The characteristic of composition or element is studied sometimes through ongoing change test.

It is illustrated by taking the compound (1z) as an example.In formula (1z), with hexagon surround α and β mark respectively with Ring α and ring β is corresponding, indicates the ring of hexatomic ring, condensed ring etc.When subscript ' x ' is 2, there are two ring α.Two ring α institute tables Two bases shown can be identical, or can also be different.The rule is suitable for any two ring α when subscript ' x ' is greater than 2.The rule Then it is also applied for other marks of bond base Z etc.The crosscutting oblique line in one side of ring β is indicated that any hydrogen on ring β can be through taking Dai Ji (- Sp-P) replaces.Subscript ' y ' indicates the quantity of replaced substituent group.When subscript ' y ' is 0, taken there is no such Generation.When subscript ' y ' is 2 or more, there are multiple substituent groups (- Sp-P) on ring β.In said case, " it can be identical, or Can be different " rule be also suitable.Furthermore the rule is also applied for situation about being used for the mark of Ra in multiple compounds.

In formula (1z), for example, the statement of " Ra and Rb be alkyl, alkoxy or alkenyl " refers to Ra and Rb independently selected from alkane In the group of base, alkoxy and alkenyl.Herein, can be identical with the base indicated by Rb by the base that Ra is indicated, or can also be different.

Sometimes at least one of compound represented by formula (1z) compound will be selected from and be referred to as " compound (1z) ". " compound (1z) " refers to the chemical combination of a kind of compound represented by formula (1z), the mixture of two kinds of compounds or three kinds or more The mixture of object.The compound represented by other formulas is also identical." it is selected from compound represented by formula (1z) and formula (2z) At least one of compound " statement refer at least one of the group selected from compound (1z) and compound (2z) chemical combination Object.

The statement of " at least one ' A ' " refers to that the quantity of ' A ' is any.The statement of " at least one ' A ' can replace through ' B ' " Refer to ' A ' quantity be one when, the position of ' A ' be it is any, ' A ' quantity for two or more when, their position It can unlimitedly select.Sometimes " at least one-CH is used₂Can replace through-O- " statement.In said case ,-CH₂-CH₂- CH₂Not adjacent-CH can be passed through₂Warp-O- replaces and is converted to-O-CH₂-O-.However, there is no adjacent-CH₂Warp-O- The case where substitution.Reason is: generation-O-O-CH in the substitution₂(peroxide).

The alkyl of liquid crystal compounds is straight-chain or branch-like, and does not include cyclic alkyl.Straight-chain alkyl is better than dividing Branch shape alkyl.These situations are also identical for the terminal groups of alkoxy, alkenyl etc.For related to 1,4- cyclohexylidene Spatial configuration (configuration), in order to improve ceiling temperature, anti-configuration is better than cis-configuration.Due to the fluoro- 1,4- of 2- Phenylene is that left and right is asymmetric, therefore exists towards left (L) and towards right (R).

It is also identical in the bilvalent radical of oxinane -2,5- diyl etc.Carbonyloxy group etc bond base (- COO- or- OCO-) also identical.

The present invention is following items etc..

A kind of 1. liquid-crystal compositions contain in the polar compound of the polymerism represented by formula (1) at least A kind of compound has nematic phase and negative dielectric anisotropy as the first additive.

In formula (1),

2. liquid-crystal compositions according to item 1 contain the polymerism represented by the formula (1-1) to formula (1-7) At least one of polar compound compound as the first additive.

Formula (1-1) is into formula (1-7), R¹For the alkyl of carbon number 1 to 10；Y¹、Y²、Y³、Y⁴、Y⁵And Y⁶For hydrogen, fluorine, methyl or Ethyl；Sp¹And Sp⁴For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,- CO- ,-COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, At least one hydrogen can replace through fluorine or chlorine；R²For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂CH₂It can Replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine.

3. liquid-crystal compositions according to any one of item 1 to item 2 of item, wherein the ratio of the first additive is 10 matter Measure % or less.

4. liquid-crystal compositions according to any one of item 1 to item 3 contain the chemical combination represented by formula (2) At least one of object compound is as first composition.

In formula (2), R⁴And R⁵For hydrogen, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 alkenyl, The alkyl for the carbon number 1 to 12 that the alkenyloxy group of carbon number 2 to 12 or at least one hydrogen replace through fluorine or chlorine；Ring B and ring D is 1,4- Cyclohexylidene, 1,4- cyclohexadienylidene, oxinane -2,5- diyl, 1,4- phenylene, at least one hydrogen replace through fluorine or chlorine Naphthalene -2,6- diyl that 1,4- phenylene, naphthalene -2,6- diyl, at least one hydrogen replace through fluorine or chlorine, chromogen alkane -2,6- diyl or Chromogen alkane -2,6- the diyl that at least one hydrogen of person replaces through fluorine or chlorine；Ring C is the fluoro- 1,4- phenylene of 2,3- bis-, the chloro- 3- of 2- is fluoro- 1,4- phenylene, the fluoro- 5- methyl-1 of 2,3- bis-, 4- phenylene, tri- fluoronaphthalene -2,6- diyl of 3,4,5-, 7,8- difluoro chromogen alkane -2, 6- diyl, 3,4,5,6- tetrafluoro fluorenes -2,7- diyl, 4,6- difluorodiphenyl and furans -3,7- diyl, 4,6- difluorodiphenyl and thiophene Pheno -3,7- diyl or 1,1,6,7- tetrafluoro indane -2,5- diyl；Z²And Z³For singly-bound, ethylidene, ethenylidene, methylene oxygroup or Carbonyloxy group；B be 0,1,2 or 3, c be 0 or 1, and b and c's and be 3 or less.

5. liquid-crystal compositions according to any one of item 1 to item 4 of item, contain selected from formula (2-1) to formula (2-35) At least one of represented compound compound is as first composition.

Formula (2-1) is into formula (2-35), R⁴And R⁵For hydrogen, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 To 12 alkenyl, carbon number 2 to 12 alkenyloxy group or the alkyl of carbon number 1 to 12 that replaces through fluorine or chlorine of at least one hydrogen.

6. liquid-crystal compositions according to item 4 or item 5 of item, wherein the ratio of first composition is 10 mass % to 90 matter Measure the range of %.

7. liquid-crystal compositions according to any one of item 1 to item 6 contain the chemical combination represented by formula (3) At least one of object compound is as second composition.

In formula (3), R⁶And R⁷For the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, at least The alkene for the carbon number 2 to 12 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that one hydrogen replaces through fluorine or chlorine replace through fluorine or chlorine Base；Ring E and ring F is 1,4- cyclohexylidene, 1,4- phenylene, the fluoro- 1,4- phenylene of 2- or the fluoro- 1,4- phenylene of 2,5- bis-；Z⁴ For singly-bound, ethylidene, ethenylidene, methylene oxygroup or carbonyloxy group；D is 1,2 or 3.

8. liquid-crystal compositions according to any one of item 1 to item 7 of item, contain selected from formula (3-1) to formula (3-13) At least one of represented compound compound is as second composition.

Formula (3-1) is into formula (3-13), R⁶And R⁷For the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to What the alkyl or at least one hydrogen for the carbon number 1 to 12 that 12 alkenyl, at least one hydrogen replace through fluorine or chlorine replaced through fluorine or chlorine The alkenyl of carbon number 2 to 12.

9. liquid-crystal compositions according to item 7 or item 8 of item, wherein the ratio of second composition is 10 mass % to 90 matter Measure the range of %.

10. liquid-crystal compositions according to any one of item 1 to item 9 contain the polymerization represented by formula (4) At least one of property compound compound is as the second additive.

In formula (4), ring G and ring J are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalene, 2- naphthalene, oxinane -2- base, 1, 3- dioxanes -2- base, pyrimidine -2-base or pyridine -2- base, in these rings, at least one hydrogen can through fluorine, chlorine, carbon number 1 to 12 alkane The alkyl for the carbon number 1 to 12 that base, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces；Ring I is 1, 4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -1,2- diyl, naphthalene -1,3- diyl, naphthalene -1,4- diyl, naphthalene - 1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- diyl, naphthalene -2,3- diyl, naphthalene -2,6- diyl, naphthalene -2,7- Diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, these In ring, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one hydrogen through fluorine Or the alkyl of the carbon number 1 to 12 of chlorine substitution replaces；Z⁵And Z⁶For singly-bound or the alkylidene of carbon number 1 to 10, the Z⁵And Z⁶In, until A few-CH₂It can replace through-O- ,-CO- ,-COO- or-OCO-, and at least one-CH₂CH₂It can be through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, at least one hydrogen can replace through fluorine or chlorine；P¹、P²And P³For polymerism base；Sp⁶、Sp⁷And Sp⁸For singly-bound or the alkylidene of carbon number 1 to 10, the Sp⁶、Sp⁷And Sp⁸In, at least one- CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can be taken through-CH=CH- or-C ≡ C- Generation, at least one hydrogen can replace through fluorine or chlorine；H is 0,1 or 2；E, f and g be 0,1,2,3 or 4, and e, f and g and for 1 with On.

11. liquid-crystal compositions according to item 10 of item, wherein in formula (4), P¹、P²And P³For selected from formula (P-1) to formula (P-5) base in polymerism base represented by.

Formula (P-1) is into formula (P-5), M⁵、M⁶And M⁷It is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine Or the alkyl of the carbon number 1 to 5 of chlorine substitution.

12. liquid-crystal compositions according to any one of item 1 to item 11 of item, contain selected from formula (4-1) to formula (4- 29) at least one of polymerizable compound represented by compound is as the second additive.

Formula (4-1) is into formula (4-29), P¹、P²And P³For in the polymerism base represented by the formula (P-1) to formula (P-3) Base；Sp⁶、Sp⁷And Sp⁸For singly-bound or the alkylidene of carbon number 1 to 10, the Sp⁶、Sp⁷And Sp⁸In, at least one-CH₂It can Replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, until Few hydrogen can replace through fluorine or chlorine；

Formula (P-1) is into formula (P-3), M⁵、M⁶And M⁷It is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine Or the alkyl of the carbon number 1 to 5 of chlorine substitution.

13. liquid-crystal compositions according to any one of item 10 to item 12, wherein the ratio of the second additive is The range of 0.03 mass % to 10 mass %.

14. liquid-crystal compositions according to any one of item 1 to item 13 of item, contain selected from formula (5-1) and formula (5-2) At least one of represented polar compound of polymerism compound is as third additive.

In formula (5-1) and formula (5-2), R⁵⁰For hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon The alkyl or at least one hydrogen for the carbon number 1 to 12 that the alkenyl of number 2 to 12, at least one hydrogen replace through fluorine or chlorine are fluorine-substituted Carbon number 2 to 12 alkenyl；R⁵¹For-OH ,-NH₂、-OR⁵³、-N(R⁵³)₂,-COOH ,-SH or-Si (R⁵³)₃Represented base, this Place, R⁵³For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂It can replace through-O-, at least one-CH₂CH₂- It can replace through-CH=CH-, in these bases, at least one hydrogen can be fluorine-substituted；Ring A⁵⁰And ring B⁵⁰For 1,4- cyclohexylidene, 1,4- Cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine - 2,5- diyls or pyridine -2,5- diyl, in these rings, at least one hydrogen can be through fluorine, the alkyl of carbon number 1 to 12, carbon number 1 to 12 The alkyl of alkoxy or the fluorine-substituted carbon number 1 to 12 of at least one hydrogen replaces；Z⁵⁰For singly-bound ,-CH₂CH₂,-CH= CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂Or-CF=CF-；Sp⁵¹、Sp⁵³And Sp⁵⁴For list The alkylidene of key or carbon number 1 to 7, in the alkylidene, at least one-CH₂It can replace through-O- ,-COO- or-OCO-, at least One-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be fluorine-substituted；Sp⁵²For singly-bound or carbon number 1 to 7 alkylidene, in the alkylidene, at least one-CH₂It can replace through-COO- or-OCO-, at least one-CH₂CH₂Can through- CH=CH- replaces, and in these bases, at least one hydrogen can be fluorine-substituted；a⁵⁰It is 0,1,2,3 or 4.

15. liquid-crystal compositions according to item 14 of item, wherein the ratio of third additive is 10 mass % or less.

16. a kind of liquid crystal display elements of item, containing liquid-crystal composition described in any one of with good grounds item 1 to item 15.

17. liquid crystal display elements according to item 16, wherein the operating mode of liquid crystal display element be IPS mode, VA mode, FFS mode or FPA mode, and the driving method of liquid crystal display element is active matrix mode.

18. a kind of liquid crystal display elements of polymer stabilizing orientating type of item, containing with good grounds item 1 to any one of item 15 institute The liquid-crystal composition stated, and the polymerizable compound in the liquid-crystal composition is polymerize.

19. a kind of liquid crystal display elements without alignment films of item, containing described in any one of with good grounds item 1 to item 15 Liquid-crystal composition, and the polymerizable compound in the liquid-crystal composition is polymerize.

A kind of 20. purposes of liquid-crystal composition of item, the liquid-crystal composition are according to any one of item 1 to item 15 Liquid-crystal composition is used in liquid crystal display element.

A kind of 21. purposes of liquid-crystal composition of item, the liquid-crystal composition are according to any one of item 1 to item 15 Liquid-crystal composition is used in the liquid crystal display element of polymer stabilizing orientating type.

A kind of 22. purposes of liquid-crystal composition of item, the liquid-crystal composition are according to any one of item 1 to item 15 Liquid-crystal composition is used in the liquid crystal display element without alignment films.

The present invention also includes following item.(a) manufacturing method of liquid crystal display element, by matching the liquid-crystal composition It is placed between two pieces of substrates, irradiation light in the state of applying voltage to the composition makes contained in the composition Polar compound with polymerism base is polymerize, to manufacture the liquid crystal display element.(b) liquid-crystal composition, Nematic ceiling temperature is 70 DEG C or more, and the optical anisotropy (measuring at 25 DEG C) under wavelength 589nm is 0.08 or more, And the dielectric anisotropy (measuring at 25 DEG C) under frequency 1kHz is -2 or less.

The present invention also includes following item.(c) composition, although in Japanese Patent Laid-Open 2006-199941 bulletin The compound (5) of record to compound (7) is the liquid crystal compounds that dielectric anisotropy is positive, but the composition contains choosing At least one of group from these compounds compound.(d) composition, containing selected from the polar compound (1) In at least two compounds.(e) composition also contains the polar compound different from the polar compound (1). (f) composition containing one kind, two kinds or at least three kinds optically active compounds, antioxidant, ultraviolet absorbing agent, disappears Photo etching, pigment, defoaming agent, the polymerizable compound different from the polymerizable compound (4), polymerization initiator, Inhibition of polymerization The additive of agent etc.(g) a kind of AM element, contains the composition.(h) a kind of element, containing the composition, and And there is TN mode, ecb mode, ocb mode, IPS mode, FFS mode, VA mode or FPA mode.(i) a kind of infiltration type member Part contains the composition.(j) being used as the composition has nematic composition.It (k) will be by the combination The composition for adding optically active compound in object and preparing is used as optical activity composition.

Composition of the invention is illustrated in the following order.First, the composition of composition is illustrated.Second, Key property and the compound to component cpd are illustrated to composition bring main effect.Third, to group The combination of ingredient in object, the preferred proportion of ingredient and its basis is closed to be illustrated.4th, to the preferred shape of component cpd State is illustrated.5th, preferred component cpd is shown.6th, the additive that can be made an addition in composition is illustrated. 7th, the synthetic method of component cpd is illustrated.Finally, the purposes to composition is illustrated.

First, the composition of composition is illustrated.The composition contains plurality of liquid crystals compound.The composition Additive can also be contained.Additive is optically active compound, antioxidant, ultraviolet absorbing agent, delustering agent, pigment, defoaming Agent, polymerizable compound, polymerization initiator, polymerization inhibitor, polar compound etc..For the viewpoint of liquid crystal compounds, The composition is classified as composition A and composition B.Composition A is in addition to containing in compound (2) and compound (3) Liquid crystal compounds other than, can also be also containing other liquid crystal compounds, additive etc.." other liquid crystal compounds " be with Compound (2) and the different liquid crystal compounds of compound (3).Such compound be the purpose for further adjustment characteristic and It is mixed in composition.

Composition B is substantially only comprising the liquid crystal compounds in compound (2) and compound (3)." substantial " Though referring to that composition B can contain additive, other liquid crystal compounds are free of.Compared with composition A, the ingredient of composition B The quantity of compound is few.In terms of reducing costs, composition B is better than composition A.It can be by mixing other liquid crystal liquid crystal properties For viewpoint of the compound further to adjust characteristic, composition A is better than composition B.

Second, key property and the compound to component cpd are mainly imitated to the characteristic bring of composition Fruit is illustrated.The key property of component cpd is summarized in table 2.In the mark of table 2, L refer to it is big or high, during M refers to Etc. degree, S refer to small or low.Mark L, M, S are the classification based on the qualitative comparison between component cpd, and mark 0 (zero) is Refer to and is less than S (small).

The characteristic of 2. compound of table

Compound	(2)	(3)
			Ceiling temperature	S~L	S~L
Viscosity	M~L	S~M
			Optical anisotropy	M~L	S~L
Dielectric anisotropy	M~L¹⁾	0
			Specific resistance	L	L

1) value of dielectric anisotropy is negative, and mark indicates the size of absolute value

When component cpd is mixed in composition, characteristic bring main effect of the component cpd to composition It is as described below.Compound (1) is adsorbed in substrate surface by the effect of polar group, and controls the orientation of liquid crystal molecule.For The desired effect of acquisition, it is desirable that compound (1) has the high compatibility with liquid crystal compounds.Think compound (1) Hexatomic ring with 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene etc, and there is rodlike molecular structure, in addition in molecular structure An end there is the structure of branch-like and compatibility can be improved, therefore be most suitable for the purpose.Compound (1) passes through polymerization Form polymer.The polymer shortens the response time of element due to stabilizing the orientation of liquid crystal molecule, and improves The image retention of image.Compound (2) improves dielectric anisotropy, and reduces lower limit temperature.Compound (3) improve ceiling temperature or Reduce viscosity.Compound (4) forms polymer by polymerization.The polymer due to stabilizing the orientation of liquid crystal molecule, Therefore shorten the response time of element, and improve the image retention of image.For the viewpoint of the orientation of liquid crystal molecule, compound (1) Polymer due to having interaction with substrate surface, therefore infer the polymer compared to compound (4) and more effective fruit.

Third is illustrated the combination of the ingredient in composition, the preferred proportion of ingredient and its basis.In composition Preferred group of ingredient be combined into compound (1)+compound (2), compound (1)+compound (2)+compound (3), compound (1) + compound (2)+compound (4), compound (1)+compound (2)+compound (3)+compound (4), compound (1)+compound (2)+compound (3)+compound (5-1), compound (1)+compound (2)+compound (3)+compound (5-2), compound (1) + compound (2)+compound (3)+compound (4)+compound (5-1) or compound (1)+compound (2)+compound (3)+change It closes object (4)+compound (5-2).

Compound (1), compound (5-1) or compound (5-2) be for control liquid crystal molecule orientation purpose and add It is added in composition.In order to be orientated liquid crystal molecule, compound (1) is preferably in a proportion of about 0.05 mass % or more, is Prevent the display of element bad, compound (1) is preferably in a proportion of about 10 mass % or less.Especially preferred ratio is about The range of 0.1 mass % to about 7 mass %.Particularly preferred ratio is range of the about 0.5 mass % to about 5 mass %.In order to It is orientated liquid crystal molecule, compound (5-1) or compound (5-2) are preferably in a proportion of about 0.05 mass % or more, in order to Prevent the display of element bad, compound (5-1) or compound (5-2) are preferably in a proportion of about 10 mass % or less.It is especially excellent The ratio of choosing is range of the about 0.1 mass % to about 7 mass %.Particularly preferred ratio is about 0.5 mass % to about 5 mass % Range.

In order to improve dielectric anisotropy, compound (2) is preferably in a proportion of about 10 mass % or more, in order to reduce lower limit Temperature, compound (2) are preferably in a proportion of about 90 mass % or less.Especially preferred ratio is about 20 mass % to about 85 matter Measure the range of %.Particularly preferred ratio is range of the about 30 mass % to about 85 mass %.

In order to improve ceiling temperature or in order to reduce viscosity, compound (3) is preferably in a proportion of about 10 mass % or more, is Raising dielectric anisotropy, compound (3) are preferably in a proportion of about 90 mass % or less.Especially preferred ratio is about 15 matter Measure the range of % to about 75 mass %.Particularly preferred ratio is range of the about 15 mass % to about 60 mass %.

In order to improve the long-term reliability of orientation, compound (4) is preferably in a proportion of about 0.03 mass % or more, in order to Prevent the display of element bad, compound (4) is preferably in a proportion of about 10 mass % or less.Especially preferred ratio is about 0.1 The range of quality % to about 2 mass %.Particularly preferred ratio is range of the about 0.2 mass % to about 1.0 mass %.

4th, the preferred configuration of component cpd is illustrated.Firstly, two kinds of liquid crystal compounds are concluded simultaneously It is illustrated.Then, with the first additive and third additive (polar compound with polymerism base), the second additive The sequence of (polymerizable compound) is illustrated.

(a) liquid crystal compounds

In formula (2) and formula (3), R⁴And R⁵For hydrogen, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 Alkenyl, carbon number 2 to 12 alkenyloxy group or the alkyl of carbon number 1 to 12 that replaces through fluorine or chlorine of at least one hydrogen.In order to improve Stability, preferred R⁴Or R⁵For the alkyl of carbon number 1 to 12, in order to improve dielectric anisotropy, preferred R⁴Or R⁵For carbon number 1 To 12 alkoxy.R⁶And R⁷For the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, at least one The alkene for the carbon number 2 to 12 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that a hydrogen replaces through fluorine or chlorine replace through fluorine or chlorine Base.In order to reduce viscosity, preferred R⁶Or R⁷For the alkenyl of carbon number 2 to 12, in order to improve stability, preferred R⁶Or R⁷For carbon The alkyl of number 1 to 12.

Preferred alkyl is methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or octyl.In order to reduce viscosity, especially Its preferred alkyl is ethyl, propyl, butyl, amyl or heptyl.

Preferred alkoxy is methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy or oxygroup in heptan.In order to Viscosity is reduced, especially preferred alkoxy is methoxy or ethoxy.

Preferred alkenyl is vinyl, 1- acrylic, 2- acrylic, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- penta Alkenyl, 2- pentenyl, 3- pentenyl, 4- pentenyl, 1- hexenyl, 2- hexenyl, 3- hexenyl, 4- hexenyl or 5- hexene Base.In order to reduce viscosity, especially preferred alkenyl is vinyl, 1- acrylic, 3- cyclobutenyl or 3- pentenyl.In these alkenyls The preferred spatial configuration of-CH=CH- depend on the position of double bond.In order to reduce the reasons such as viscosity, in 1- acrylic, 1- butylene It is preferably anti-configuration in the alkenyl of base, 1- pentenyl, 1- hexenyl, 3- pentenyl, 3- hexenyl etc.2- cyclobutenyl, It is preferably cis-configuration in the alkenyl of 2- pentenyl, 2- hexenyl etc.

Preferred alkenyloxy group is ethyleneoxy, allyloxy, 3- butenyloxy, 3- amylene oxygroup or 4- amylene oxygroup.For Reduction viscosity, especially preferred alkenyloxy group are allyloxy or 3- butenyloxy.

The preference for the alkyl that at least one hydrogen replaces through fluorine or chlorine is methyl fluoride, 2- fluoro ethyl, 3- fluoropropyl, 4- fluorine fourth Base, 5- fluorine amyl group, 6- fluorine hexyl, 7- fluorine heptyl or 8- fluorine octyl.In order to improve dielectric anisotropy, particularly preferred example is 2- fluorine Ethyl, 3- fluoropropyl, 4- fluorine butyl or 5- fluorine amyl group.

The preference for the alkenyl that at least one hydrogen replaces through fluorine or chlorine is 2,2- difluoroethylene base, the fluoro- 2- propylene of 3,3- bis- Base, the fluoro- 3- cyclobutenyl of 4,4- bis-, the fluoro- 4- pentenyl of 5,5- bis- or the fluoro- 5- hexenyl of 6,6- bis-.It is especially excellent in order to reduce viscosity Selecting example is 2,2- difluoroethylene base or the fluoro- 3- cyclobutenyl of 4,4- bis-.

Ring B and ring D is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, oxinane -2,5- diyl, 1,4- phenylene, extremely Naphthalene-the 2,6- of 1,4- phenylene, naphthalene -2,6- diyl, at least one hydrogen through fluorine or chlorine substitution that few hydrogen replaces through fluorine or chlorine Chromogen alkane -2,6- the diyl that diyl, chromogen alkane -2,6- diyl or at least one hydrogen replace through fluorine or chlorine." at least one hydrogen The preference of the 1,4- phenylene replaced through fluorine or chlorine " is that the fluoro- 1,4- phenylene of 2-, the fluoro- 1,4- phenylene of 2,3- bis- or 2- are chloro- The fluoro- 1,4- phenylene of 3-.In order to reduce viscosity, preferred ring B or ring D are 1 or 4 cyclohexylidene, in order to improve dielectric respectively to different Property, preferred ring B or ring D are oxinane -2,5- diyl, and in order to improve optical anisotropy, preferred ring B or ring D are 1, 4- phenylene.

Ring C is the fluoro- 1,4- phenylene of 2,3- bis-, the fluoro- 1,4- phenylene of the chloro- 3- of 2-, the fluoro- 5- methyl-1 of 2,3- bis-, and 4- is sub- Phenyl, tri- fluoronaphthalene -2,6- diyl of 3,4,5-, 7,8- difluoro chromogen alkane -2,6- diyl, 3,4,5,6- tetrafluoro fluorenes -2,7- diyl (FLF4), 4,6- difluorodiphenyl and furans -3,7- diyl (DBFF2), 4,6- difluorodiphenyl bithiophene -3,7- diyl (DBTF2) Or 1,1,6,7- tetrafluoro indane -2,5- diyl (InF4).

In order to improve dielectric anisotropy, preferred ring C is the fluoro- Isosorbide-5-Nitrae-phenylene of 2,3- bis-.

Ring E and ring F is 1,4- cyclohexylidene, the bis- fluoro- Asia 1,4- benzene of 1,4- phenylene, the fluoro- 1,4- phenylene of 2- or 2,5- Base.In order to reduce viscosity or in order to improve ceiling temperature, preferred ring E or ring F are 1 or 4 cyclohexylidene, in order to reduce lower limit temperature Degree, preferred ring E or ring F are Isosorbide-5-Nitrae-phenylene.

Z²And Z³For singly-bound, ethylidene, ethenylidene, methylene oxygroup or carbonyloxy group.In order to reduce viscosity, preferred Z²Or Z³For singly-bound, in order to improve dielectric anisotropy, preferred Z²Or Z³For methylene oxygroup.Z⁴For singly-bound, ethylidene, ethenylidene, Methylene oxygroup or carbonyloxy group.In order to reduce viscosity, preferred Z⁴For singly-bound.

B be 0,1,2 or 3, c be 0 or 1, and b and c's and be 3 or less.In order to reduce viscosity, preferred b is 1, in order to Ceiling temperature is improved, preferred b is 2 or 3.In order to reduce viscosity, preferred c is 0, and in order to reduce lower limit temperature, preferred c is 1.D is 1,2 or 3.In order to reduce viscosity, preferred d is 1, and in order to improve ceiling temperature, preferred d is 2 or 3.

(b) the first additive and third additive

In formula (1), X¹For-OH ,-NH₂、-OR³、-N(R³)₂,-COOH ,-SH or-Si (R³)₃.Herein, R³For hydrogen or carbon number 1 To 10 alkyl, in the alkyl, at least one-CH₂It can replace through-O-, at least one-CH₂CH₂It can be taken through-CH=CH- In generation, in these bases, at least one hydrogen can replace through fluorine or chlorine.For the viewpoint of the high solubility to liquid-crystal composition, X¹ Particularly preferably-OH or-NH₂.- OH has high anchor force, therefore is better than-O- ,-CO- or-COO-.Particularly preferably have The base of multiple hetero atoms (nitrogen, oxygen).Even if the compound with such polar group is that low concentration is also effective.Compound (1) is preferred For to ultraviolet light or thermostabilization.When making an addition to compound (1) in composition, the compound does not reduce element preferably Voltage retention.Compound (1) preferably has low volatility.Preferred molal weight is 130g/mol or more.It is especially excellent The molal weight of choosing is the range of 150g/mol to 700g/mol.Preferred compound (1) has acryloxy (- OCO-CH =CH₂), methacryloxy (- OCO- (CH₃) C=CH₂) etc polymerism base.

R¹For hydrogen or the alkyl of carbon number 1 to 15, in the alkyl, at least one-CH₂It can replace through-O- or-S-, at least One-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, at least one hydrogen can replace through fluorine or chlorine.Preferred R¹For carbon number 1 To 10 alkyl, the alkenyl of carbon number 2 to 10 or the alkoxy of carbon number 1 to 9.Especially preferred R¹For the alkyl of carbon number 1 to 10.R² For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂It can replace through-O- or-S-, at least one-CH₂CH₂- It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred R²For carbon number 1 to 3 Alkyl.Especially preferred R²For methyl.

Ring A¹And ring A²It is sub- for 1,2- cyclopropylidene, the Asia 1,3- cyclobutyl, 1,3- cyclopentylene, 1,4- cyclohexylidene, 1,4- Suberyl, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, decahydronaphthalene -2,6- diyl, 1,2,3,4- naphthane - 2,6- diyls, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, In these rings, at least one hydrogen can through fluorine, chlorine, the alkyl of carbon number 1 to 10, the alkenyl of carbon number 2 to 10, carbon number 1 to 9 alkoxy Or the alkenyloxy group of carbon number 2 to 9 replaces, in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred ring A¹Or ring A²It is 1, 4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, oxinane -2,5- diyl, 1,3- bis- are disliked Alkane -2,5- diyl, pyrimidine -2,5- diyl, pyridine -2,5- diyl or 3- ethyl-Isosorbide-5-Nitrae-phenylene, particularly preferred ring A¹Or ring A²For 1,4- cyclohexylidene, 1,4- phenylene, the fluoro- 1,4- phenylene of 2-, naphthalene -2,6- diyl or 3- ethyl -1,4- phenylene.

Z¹For singly-bound or the alkylidene of carbon number 1 to 6, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least One hydrogen can replace through fluorine or chlorine.Preferred Z¹For singly-bound ,-CH₂CH₂-、-(CH₂)₄,-CH=CH- ,-C ≡ C- ,-COO- ,- OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂Or-CF=CF-.Especially preferred Z¹For singly-bound.

Sp¹、Sp²、Sp³And Sp⁴For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂It can Replace through-O- ,-CO- ,-COO- ,-OCO- or-OCOO-, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, this In a little bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Sp¹、Sp²、Sp³And Sp⁴For singly-bound or the alkylene of carbon number 1 to 5 Base, in the alkylidene, at least one-CH₂It can replace through-O-, at least one-CH₂CH₂It can replace through-CH=CH-.Especially Preferred Sp¹、Sp²、Sp³And Sp⁴For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂Can through- O- replaces.

Sp⁵For the alkylidene of carbon number 2 to 10, in the alkylidene, at least one-CH₂It can replace through-O-.Preferred Sp⁵ For-CH₂CH₂-。

M¹、M²、M³And M⁴The carbon number replaced for hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine or chlorine 1 to 5 alkyl.Preferred M¹、M²、M³And M⁴For hydrogen or the alkyl of carbon number 1 to 3.

A is 0,1,2,3 or 4.Preferred a is 1 or 2.

Formula (1-1) is into formula (1-7), Y¹、Y²、Y³、Y⁴、Y⁵And Y⁶For hydrogen, fluorine, methyl or ethyl.

In formula (5-1) and formula (5-2), R⁵⁰For hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon The alkyl or at least one hydrogen for the carbon number 1 to 12 that the alkenyl of number 2 to 12, at least one hydrogen replace through fluorine or chlorine are fluorine-substituted Carbon number 2 to 12 alkenyl.Preferred R⁵⁰For the alkyl of carbon number 1 to 10.R⁵¹For-OH ,-NH₂、-OR⁵³、-N(R⁵³)₂、- COOH ,-SH or-Si (R⁵³)₃Represented base, herein, R⁵³For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one- CH₂It can replace through-O-, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can take through fluorine Generation.For the viewpoint of the high solubility to liquid-crystal composition, R⁵¹Preferably-OH or-NH₂。

Ring A⁵⁰And ring B⁵⁰For 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, tetrahydro Pyrans -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, in these rings, at least One hydrogen can be through fluorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or the fluorine-substituted carbon number 1 of at least one hydrogen Alkyl to 12 replaces.

Z⁵⁰For singly-bound ,-CH₂CH₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,-CF₂O-、-OCF₂-、-CH₂O-、- OCH₂Or-CF=CF-.Particularly preferred Z⁵⁰For singly-bound.

Sp⁵¹、Sp⁵³And Sp⁵⁴For singly-bound or the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂Can through- O- ,-COO- or-OCO- replace, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be through fluorine Replace.Sp⁵²For singly-bound or the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂It can be taken through-COO- or-OCO- Generation, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be fluorine-substituted.Preferred Sp⁵¹、 Sp⁵²、Sp⁵³And Sp⁵⁴For singly-bound or the alkylidene of carbon number 1 to 7.

a⁵⁰It is 0,1,2,3 or 4, preferably 1 or 2.

(c) the second additive

In formula (4), ring G and ring J are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalene, 2- naphthalene, oxinane -2- base, 1, 3- dioxanes -2- base, pyrimidine -2-base or pyridine -2- base, in these rings, at least one hydrogen can through fluorine, chlorine, carbon number 1 to 12 alkane The alkyl for the carbon number 1 to 12 that base, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces.Preferred ring G or ring J is phenyl.Ring I is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -1,2- diyl, naphthalene -1,3- Diyl, naphthalene -1,4- diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- diyl, naphthalene -2,3- diyl, Naphthalene -2,6- diyl, naphthalene -2,7- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or Pyridine -2,5- diyl, in these rings, at least one hydrogen can through fluorine, chlorine, the alkyl of carbon number 1 to 12, carbon number 1 to 12 alkoxy, Or the alkyl of carbon number 1 to 12 of at least one hydrogen through fluorine or chlorine substitution replaces.Preferred ring I is that 1,4- phenylene or 2- are fluoro- 1,4- phenylene.

Z⁵And Z⁶For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,- CO- ,-COO- or-OCO- replace, and at least one-CH₂CH₂It can be through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Z⁵Or Z⁶For list Key ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.Especially preferred Z⁵Or Z⁶For singly-bound.

P¹、P²And P³For polymerism base.Preferred P¹、P²Or P³For the group of the base represented by the formula (P-1) to formula (P-5) Polymerism base in group.Especially preferred P¹、P²Or P³For base represented by formula (P-1), formula (P-2) or formula (P-3).It is especially excellent The P of choosing¹、P²Or P³For base represented by formula (P-1) or formula (P-2).Most preferred P¹、P²Or P³For base represented by formula (P-1). Preferred base represented by formula (P-1) is-OCO-CH=CH₂Or-OCO-C (CH₃)=CH₂.Formula (P-1) to formula (P-5) wave Line indicates the position of bond.

Formula (P-1) is into formula (P-5), M⁵、M⁶And M⁷It is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine Or the alkyl of the carbon number 1 to 5 of chlorine substitution.In order to improve reactivity, preferred M⁵、M⁶Or M⁷For hydrogen or methyl.Especially preferred M⁵ For hydrogen or methyl, and especially preferred M⁶Or M⁷For hydrogen.

Sp⁶、Sp⁷And Sp⁸For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-COO- ,-OCO- or-OCOO- replace, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, these bases In, at least one hydrogen can replace through fluorine or chlorine.Preferred Sp⁶、Sp⁷Or Sp⁸For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂-、- COO- ,-OCO- ,-CO-CH=CH- or-CH=CH-CO-.Especially preferred Sp⁶、Sp⁷Or Sp⁸For singly-bound.

H is 0,1 or 2.Preferred h is 0 or 1.E, f and g be 0,1,2,3 or 4, and e, f and g and be 1 or more.It is preferred that E, f or g be 1 or 2.

5th, preferred component cpd is shown.Preferred compound (1) is compound (1-1) described in item 2 to chemical combination Object (1-7).In these compounds, preferably at least one of the first additive is compound (1-1) to compound (1-3).It is excellent At least two of the first additive are selected as the combination of compound (1-1) and compound (1-2).

Preferred compound (2) is compound (2-1) described in item 5 to compound (2-33).In these compounds, preferably At least one for first composition is compound (2-1), compound (2-3), compound (2-6), compound (2-8), compound (2-10), compound (2-13), compound (2-14) or compound (2-18).Preferably at least two of first composition are chemical combination Object (2-1) and compound (2-8), compound (2-1) and compound (2-14), compound (2-3) and compound (2-8), chemical combination Object (2-3) and compound (2-10), compound (2-3) and compound (2-14), compound (2-6) and compound (2-8), chemical combination Object (2-6) and compound (2-10), compound (2-6) and compound (2-18) or compound (2-10) and compound (2-14) Combination.

Preferred compound (3) is compound (3-1) described in item 8 to compound (3-13).In these compounds, preferably At least one for second composition is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-8) or compound (3-9).Preferably at least two of second composition are compound (3-1) and compound (3-3), compound The combination of (3-1) and compound (3-5) or compound (3-1) and compound (3-6).

Preferred compound (4) is compound (4-1) described in item 12 to compound (4-29).It is excellent in these compounds Be selected as the second additive at least one be compound (4-1), compound (4-2), compound (4-24), compound (4-25), Compound (4-26), compound (4-27) or compound (4-29).Preferably at least two of the second additive are compound (4- And compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24), compound (4- 1) And compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26) or compound 2) The combination of (4-18) and compound (4-24).

6th, the additive other than the first additive that can be made an addition in composition is illustrated.Such additive is Optically active compound, antioxidant, ultraviolet absorbing agent, delustering agent, pigment, defoaming agent, polymerizable compound, polymerization cause Agent, polymerization inhibitor, polar compound etc..Torsion angle is assigned for the helical structure of liquid crystal molecule is caused (torsionangle) purpose, and optically active compound is made an addition in composition.The example of such compound is chemical combination Object (6-1) is to compound (6-5).Optically active compound is preferably in a proportion of about 5 mass % or less.Especially preferred ratio is The range of about 0.01 mass % to about 2 mass %.

The reduction of the specific resistance as caused by the heating in atmosphere or in order to after by element long-time use in order to prevent, Not only at room temperature, and close to ceiling temperature at a temperature of also maintain big voltage retention, and antioxidant is added It is added in composition.The preference of antioxidant is compound (7-1) to compound (7-3) etc..

Compound (7-2) is since volatility is small, therefore for after by element long-time use, not only at room temperature, but also Close to ceiling temperature at a temperature of also maintain for big voltage retention effectively.It is anti-oxidant in order to obtain the effect Agent is preferably in a proportion of about 50ppm or more, in order not to reduce ceiling temperature or in order not to improve lower limit temperature, antioxidant it is excellent Selecting ratio is about 600ppm or less.Especially preferred ratio is range of the about 100ppm to about 300ppm.

The preference of ultraviolet absorbing agent is benzophenone derivates, benzoate derivatives, triazole derivative etc..Separately Outside, amine etc with steric hindrance light stabilizer it is also preferred that.The preference of light stabilizer is compound (8-1) to compound (8- 16) etc..In order to obtain the effect, these absorbents or stabilizer are preferably in a proportion of about 50ppm or more, on reducing Limit temperature or in order not to improve lower limit temperature, these absorbents or stabilizer are preferably in a proportion of about 10000ppm or less.Especially Preferred ratio is range of the about 100ppm to about 10000ppm.

Delustering agent is the light energy absorbed by receiving liquid crystal compounds, and is converted to thermal energy to prevent liquid crystal liquid crystal property The compound of the decomposition of compound.The preference of delustering agent is compound (9-1) to compound (9-7) etc..It is described in order to obtain Effect, these delustering agents are preferably in a proportion of about 50ppm or more, in order not to improve lower limit temperature, the preferred ratio of these delustering agents Example is about 20000ppm or less.Especially preferred ratio is range of the about 100ppm to about 10000ppm.

In order to be suitable for the element of host and guest (guest host, GH) mode, and by azo system pigmen, anthraquinone system pigment etc. it The dichroism pigment (dichroic dye) of class makes an addition in composition.Pigment is preferably in a proportion of about 0.01 mass % to about 10 The range of quality %.

It is bubbled in order to prevent, and the defoaming agents such as dimethyl silicone oil, methylphenylsilicone oil is made an addition in composition.For The acquisition effect, defoaming agent are preferably in a proportion of about 1ppm or more, show bad, the preferred proportion of defoaming agent in order to prevent It is about 1000ppm or less.Especially preferred ratio is range of the about 1ppm to about 500ppm.

In order to be suitable for the element of polymer stabilizing orientation (PSA) type, and use polymerizable compound.Compound (1) is changed It closes object (4), compound (5-1) and compound (5-2) and is suitable for the purpose.It can also be by compound (1), compound (4), chemical combination Object (5-1) and compound (5-2) and from compound (1), compound (4), compound (5-1) and compound (5-2) it is different Other polymerizable compounds make an addition in composition together.The preference of such polymerizable compound is acrylate, methyl-prop Olefin(e) acid ester, vinyl compound, ethyleneoxy compounds, propenyl ether, epoxide (oxirane, oxa- ring fourth Alkane), the compounds such as vinyl ketone.Particularly preferred example is acrylate or methacrylate.By changing compound (1), changing Close object (4), compound (5-1) and compound (5-2) type, or by with it is appropriate than by other polymerizable compounds with Compound (1), compound (4), compound (5-1) and compound (5-2) are combined, and can adjust the reaction of polymerizable compound The pre-tilt angle of property or liquid crystal molecule.By optimizing pre-tilt angle, it may achieve the short response time of element.Liquid crystal molecule takes To stabilisation, therefore it may achieve big contrast ratio or long-life.

The polymerizable compound is irradiated by ultraviolet light to be polymerize.It can also be in the initiator appropriate such as Photoepolymerizationinitiater initiater In the presence of polymerize.The appropriate type and appropriate amount of felicity condition, initiator for being polymerize have been this field Known to technical staff, and it is described in the literature.Such as gorgeous good solid (Irgacure) 651 (registrar as Photoepolymerizationinitiater initiater Mark；BASF (BASF)), gorgeous good solid (Irgacure) 184 (registered trademark；BASF (BASF)) or moral is securely (Darocur) 1173 (registered trademarks；BASF (BASF)) it is suitable for free radical polymerization.Quality based on polymerizable compound, photopolymerization cause The range for being preferably in a proportion of about 0.1 mass % to about 5 mass % of agent.Especially preferred ratio is about 1 mass % to about 3 matter Measure the range of %.

In the keeping polymerizable compound, it polymerize in order to prevent, polymerization inhibitor can also be added.Polymerizable compound Usually made an addition in composition with the state for not removing polymerization inhibitor.The example of polymerization inhibitor is hydroquinone, methyl Hydroquinone derivative, 4- tert-butyl catechol, 4- metoxyphenol, phenthazine of hydroquinone etc etc..

Polar compound is with polar organic compound.Herein, not comprising the compound with ionic bond.Oxygen, sulphur And the electrical property of the atom of nitrogen etc is partially negative and there is the tendency with partial negative charge.Carbon and hydrogen are neutral or exist with portion Divide the tendency of positive charge.Polarity is unequally distributed and generates between atom not of the same race because of Partial charge in compound. For example, polar compound has-OH ,-COOH ,-SH ,-NH₂At least one of the part-structure of, > NH, > N- etc.

7th, the synthetic method of component cpd is illustrated.These compounds can be synthesized using known method. Illustrate synthetic method.The synthetic method of compound (1) is recorded in the item of embodiment.Compound (2-1) is special using Japan The method recorded in sharp special table level 2-503441 bulletin synthesizes.Compound (3-5) is to utilize Japanese Patent Laid-Open No. Sho 57- The method recorded in No. 165328 bulletins synthesizes.Compound (4-18) is to utilize Japanese Patent Laid-Open 7-101900 bulletin The method of middle record synthesizes.Compound (7-1) can be from Sigma-Aldrich (Sigma-Aldrich Corporation it) obtains.Compound (7-2) etc. is closed using the method recorded in No. 3660505 specifications of United States Patent (USP) At.

The compound for not recording synthetic method can be synthesized using the method that following Cheng Shuzhong is recorded: " organic synthesis " (Organic Syntheses, John Wei Li father and son publishing company (John Wiley&Sons, Inc.)), " organic reaction " (Organic Reactions, John Wei Li father and son publishing company), " comprehensive organic synthesis " (Comprehensive Organic Synthesis, Pei Geman publishing company (Pergamon Press)), new experimental chemistry lecture (ball kind) etc..Composition is to utilize Well known method is prepared by the compound obtained in this way.For example, component cpd is mixed, then pass through heating And it is mutually dissolved it.

Finally, the purposes to composition is illustrated.Most composition have about -10 DEG C of lower limit temperatures below, The optical anisotropy of the range of about 70 DEG C or more of ceiling temperature and about 0.07 to about 0.20.Control composition can be passed through It closes the ratio of object or passes through and mix other liquid crystal compounds, to prepare the optics of the range with about 0.08 to about 0.25 Anisotropic composition.And then can also be prepared by trial and error with about 0.10 to about 0.30 range optics respectively to Anisotropic composition.Element containing the composition has big voltage retention.The composition is suitable for AM element.Institute State AM element of the composition particularly suitable for infiltration type.The composition can be used as having nematic composition, Neng Goutong It crosses addition optically active compound and is used as optical activity composition.

The composition can be used in AM element.And then it also can be used in PM element.The composition can be used in having The AM element and PM element of PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA isotype.Particularly preferably for TN, The AM element of OCB, IPS mode or FFS mode.In AM element with IPS mode or FFS mode, when not applying voltage, liquid The orientation of brilliant molecule can be parallel with glass substrate, or can also be vertical.These elements can be reflection-type, infiltration type or semi-permeable Type.It is preferably used for the element of infiltration type.Also it can be used in amorphous silicon-TFT element or polysilicon-TFT element.It can also will be described Composition is used to carry out microencapsulation (microencapsulation) and the nematic curved arrangement phase (nematic of production Curvilinear aligned phase, NCAP) type element or formed made of three-dimensional netted macromolecule in the composition The element of polymer dispersion (polymer dispersed, PD) type.

An example for manufacturing the method for the element of polymer stabilizing orientating type is as described below.Prepare the member including two pieces of substrates Part, two pieces of substrates are referred to as array substrate and colored filter substrate.The substrate has alignment films.The substrate is extremely Few one piece has electrode layer.Liquid crystal compounds mixing is prepared into liquid-crystal composition.Polymerism is added in the composition Compound.Additive can be optionally added in turn.The composition is injected into element.It is alive being applied to the element Light irradiation is carried out under state.Preferably ultraviolet light.It polymerize polymerizable compound by light irradiation.Pass through the polymerization And generate the composition containing polymer.The element of polymer stabilizing orientating type is sequentially to manufacture as described above.

In the sequence, when applying voltage, liquid crystal molecule is orientated by the effect of alignment films and electric field.According to described in Orientation, the molecule of polymerizable compound are also orientated.Due to polymerizable compound be in this condition by ultraviolet light come It is polymerize, therefore generates the polymer for maintaining the orientation.By the effect of the polymer, the response time of element shortens. Since the running that the image retention of image is liquid crystal molecule is bad, therefore by the effect of the polymer, image retention is also improved simultaneously. Furthermore also the polymerizable compound in composition can be made to be polymerize in advance, the composition is configured at liquid crystal display member Between the substrate of part.

In the polar compounds with polymerism base of use compound (1), compound (5-1) and compound (5-2) etc In the case where object (that is, polymerizable compound), alignment films are not needed on the substrate of element.Element foundation without alignment films The sequence recorded in the first two paragraph is not by having the substrate manufacture of alignment films.

In the sequence, because of polar group and substrate surface phase occurs for compound (1), compound (5-1) and compound (5-2) Interaction and arranged on substrate.According to the arrangement, liquid crystal molecule is orientated.When applying voltage, further promote Into the orientation of liquid crystal molecule.Since polymerism base is to be polymerize in this condition by ultraviolet light, therefore generate and maintain institute State the polymer of orientation.By the effect of the polymer, the orientation of liquid crystal molecule is additionally stabilized, the response time of element Shorten.Since the running that the image retention of image is liquid crystal molecule is bad, therefore by the effect of the polymer, image retention also obtains simultaneously Improve.

[embodiment]

The present invention is further described in detail by embodiment.The present invention is not restricted by the embodiments.This hair The bright mixture comprising composition M1 and composition M2.The present invention also include by at least two of the composition of embodiment mixing and At mixture.Synthesized compound is by nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) analysis etc. Method is identified.The characteristic of compound, composition and element is measured by following methods.

NMR analysis: the DRX-500 manufactured when measurement using this guest (Bruker BioSpin) company of Brooker Baier.¹H- In the measurement of NMR, sample is made to be dissolved in CDCl₃Etc. in deuterates solvent, at room temperature with 500MHz, the item that cumulative number is 16 times Part is measured.Use tetramethylsilane as internal standard.¹⁹In the measurement of F-NMR, CFCl is used₃As internal standard, with Cumulative number 24 times carries out.In the explanation of NMR spectrum, s refers to unimodal (singlet), and d refers to doublet (doublet), t refers to triplet (triplet), and q refers to quartet (quartet), and quin refers to quintet (quintet), Sex refers to sextet (sextet) that m refers to multiplet (multiplet), and br refers to broad peak (broad).

Gas chromatographic analysis: the GC-14B type gas chromatograph manufactured when measurement using Shimadzu Seisakusho Ltd..Carrier gas is Helium (2mL/min).Sample evaporation chamber is set as 280 DEG C, will test device (flame ionization detector (flame Ionization detector, FID)) it is set as 300 DEG C.It carries out limited using Agilent Technologies when the separation of component cpd Capillary column DB-1 (length 30m, internal diameter 0.32mm, the film thickness 0.25 of company (Agilent Technologies Inc.) manufacture μm；Fixed liquid phase is dimethyl polysiloxane；It is nonpolarity).After the tubing string is kept for 2 minutes at 200 DEG C, with 5 DEG C/min's Ratio is warming up to 280 DEG C.After sample is prepared into acetone soln (0.1 mass %), its 1 μ L is injected into sample evaporation chamber. Record is calculated as the C-R5A type chromatopac (Chromatopac) or its same product of Shimadzu Seisakusho Ltd.'s manufacture.Gas phase obtained Chromatogram shows the retention time of peak value corresponding with component cpd and the area of peak value.

Chloroform, hexane etc. can be used in solvent for diluting sample.In order to separate component cpd, can be used as follows Capillary column.HP-1 (the length 30m, internal diameter of Anjelen Sci. & Tech. Inc (Agilent Technologies Inc.) manufacture 0.25 μm of 0.32mm, film thickness), Rui Si Imtech (Restek Corporation) manufacture Rtx-1 (length 30m, internal diameter 0.25 μm of 0.32mm, film thickness), SGE international corporation, Australia (SGE International Pty.Ltd) manufacture BP-1 (length 30m, internal diameter 0.32mm, 0.25 μm of film thickness).For the purpose for the overlapping for preventing compound peak value, Shimadzu production can be used Manufactured capillary column CBP1-M50-025 (length 50m, internal diameter 0.25mm, 0.25 μm of film thickness).

The ratio of liquid crystal compounds contained in composition can be calculated using method as described below.Utilize gas phase Chromatograph (FID) analyzes the mixture of liquid crystal compounds.The area ratio of peak value in gas chromatogram is equivalent to The ratio of liquid crystal compounds.It, can be by the correction factor of various liquid crystal compounds when the capillary column that text is recorded in use It is considered as 1.Therefore, the ratio (quality %) of liquid crystal compounds can be calculated according to the area ratio of peak value.

It measures sample: when measuring the characteristic of composition and element, composition being directly used as sample.In measurement compound Characteristic when, prepare measurement sample by the way that the compound (15 mass %) to be mixed in mother liquor brilliant (85 mass %). According to the value obtained by measurement, the characteristic value of compound is calculated using extrapolation (extrapolation method). (extrapolated value)={ (measured value of sample) -0.85 × (measured value of mother liquor crystalline substance) }/0.15.Under the ratio, smectic phase When (or crystallization) is precipitated at 25 DEG C, by the ratio of compound and mother liquor crystalline substance with 10 mass %:90 mass %, 5 mass %:95 matter Measure the sequence change of %, 1 mass %:99 mass %.Ceiling temperature relevant to compound, light are found out using the extrapolation Learn the value of anisotropy, viscosity and dielectric anisotropy.

It is brilliant using following mother liquors.The ratio of component cpd is indicated with quality %.

Measuring method: the measurement of characteristic is carried out using following methods.These methods are Japan Electronics information technology mostly Industry association (Japan Electronics and Information Technology Industries Association； Referred to as JEITA) method recorded in the JEITA standard (JEITAED-2521B) formulated of review or side made of being modified Method.Thin film transistor (TFT) (TFT) is not installed on the TN element of measurement.

(1) nematic ceiling temperature (NI；DEG C): it is placed on the hot plate for the melting point apparatus for having petrographic microscope Sample is heated with the speed of 1 DEG C/min.Measure sample a part by nematic phase change be isotropic liquid when temperature Degree.Sometimes nematic ceiling temperature is referred to as " ceiling temperature ".

(2) nematic lower limit temperature (T_C；DEG C): there will be nematic sample to be put into vial, in 0 DEG C, -10 DEG C, -20 DEG C, take care of 10 days in the freezer units of -30 DEG C and -40 DEG C after, observe liquid crystalline phase.For example, when sample is kept at -20 DEG C Nematic state, and variation is for crystallization or when smectic phase at -30 DEG C, by T_CIt is recorded as < -20 DEG C.It sometimes will be nematic Lower limit temperature is referred to as " lower limit temperature ".

(3) viscosity (bulk viscosity；η；It is measured at 20 DEG C；MPas): Tokyo gauge share limited public affairs are used when measurement Take charge of the E type rotational viscometer of manufacture.

(4) viscosity (rotary viscosity；γ1；It is measured at 25 DEG C；MPas): technology (TOY in Dongyang is used when measurement OCorporation) the rotational viscosity rate of limited liability company measures system LCM-2 type.It is (single at the interval of two panels glass substrate First gap) it is to inject sample in 10 μm of VA element.Rectangular wave (55V, 1ms) is applied to the element.Measurement is applied by described The peak point current (peak current) and time to peak (peak of transient current (transient current) for adding and generating time).The value of rotary viscosity is obtained using these measured values and dielectric anisotropy.Dielectric anisotropy is to utilize measurement (6) method recorded in measures.

(5) optical anisotropy (refractive anisotrop；Δn；Measured at 25 DEG C): using the light of wavelength 589nm, benefit It is measured with the Abbe refractometer for being equipped with polarizer on ocular lens.The surface of headprism is rubbed to a direction Afterwards, sample is added dropwise on headprism.Refractive index n ∥ is measured at the direction of polarisation and the parallel direction of friction.Folding Penetrating rate n ⊥ is measured at the direction of polarisation and the vertical direction of friction.Optically anisotropic value is according to Δ n=n The formula of ∥-n ⊥ calculates.

(6) dielectric anisotropy (Δ ε；Measured at 25 DEG C): the value of dielectric anisotropy is according to Δ ε=ε ∥-ε ⊥ Formula calculate.Measure dielectric constant (ε ∥ and ε ⊥) as follows.

1) octadecyl triethoxysilicane the measurement of dielectric constant (ε ∥): is coated on the glass substrate through sufficiently cleaning Ethyl alcohol (20mL) solution of alkane (octadecyl triethoxysilane) (0.16mL).Glass substrate is revolved using rotator After turning, heated 1 hour at 150 DEG C.Examination is put into the VA element that the interval (cell gap) of two panels glass substrate is 4 μm Sample, using the bonding agent hardened with ultraviolet light by the component seal.To the element apply sine wave (0.5V, 1kHz), the dielectric constant (ε ∥) on the long axis direction of liquid crystal molecule is measured after 2 seconds.

2) measurement of dielectric constant (ε ⊥): polyimide solution is coated on the glass substrate through sufficiently cleaning.It will be described After glass substrate calcining, friction treatment is carried out to alignment films obtained.It is 9 at the interval (cell gap) of two panels glass substrate μm and torsion angle be to inject sample in 80 degree of TN element.Sine wave (0.5V, 1kHz) is applied to the element, is measured after 2 seconds Dielectric constant (ε ⊥) on the short-axis direction of liquid crystal molecule.

(7) starting voltage (Vth；It is measured at 25 DEG C；V): being manufactured when measurement using great Zhong electronics limited liability company LCD5100 type luminance meter.Light source is halogen lamp.At the interval (cell gap) of two panels glass substrate be 4 μm and frictional direction is It is put into sample in the antiparallel VA element for normally showing black mode (normally black mode), use is carried out with ultraviolet light The bonding agent of hardening is by the component seal.To the element apply voltage (60Hz, rectangular wave) be as unit of 0.02V from 0V periodically increases to 20V.At this point, from vertical direction to element irradiation light, measurement penetrates the light quantity of element.It is formed in described Transmitance is 100% when light quantity reaches maximum, and voltage-transmittance curve that transmitance is 0% when the light quantity is minimum. Starting voltage is voltage when reaching 10% by transmitance to indicate.

(8) voltage retention (initial VHR；It is measured at 60 DEG C；%): the TN element for measurement takes with polyimides To film, and the interval (cell gap) of two panels glass substrate is 3.5 μm.The element utilizes after injecting sample with ultraviolet Bonding agent that line is hardened seals.Apply pulse voltage (1V, 60 microseconds) to the TN element to charge.Utilize high speed Potentiometer measures the voltage of decaying in a period of 166.6 milliseconds, finds out the face between the voltage curve of unit period and horizontal axis Product A.Area B is area when voltage is not decayed.Voltage retention is to be indicated by area A relative to the percentage of area B.

(9) voltage retention (UV-VHR；It is measured at 60 DEG C；%): ultraviolet light is irradiated to the TN element for being injected with sample Afterwards, voltage retention is measured, the stability to ultraviolet light is evaluated.TN element for measurement has alignment film of polyimide, and And cell gap is 3.5 μm.Sample is injected in the element, uses UV2 as light source, irradiates the light of 5mW 166.6 minutes. Thereafter, the measurement of UV-VHR is carried out with determination condition identical with initial VHR.Composition with big UV-VHR is to ultraviolet light With big stability.UV-VHR is preferably 90% or more, and especially preferably 95% or more.

(10) voltage retention (heating VHR；It is measured at 60 DEG C；%): the TN element of sample will be injected in 120 DEG C of perseverances In warm slot after heating 20 hours, voltage retention is measured, evaluates the stability to heat.TN element for measurement has polyamides sub- Amine alignment films, and cell gap is 3.5 μm.Sample is injected in the element, is heated 20 hours in 120 DEG C of thermostats. Thereafter, the measurement of heating VHR is carried out with determination condition identical with initial VHR.Composition with big heating VHR has heat There is big stability.Heating VHR is preferably 90% or more, and especially preferably 95% or more.

(11) response time (τ；It is measured at 25 DEG C；Ms): being manufactured when measurement using great Zhong electronics limited liability company LCD5100 type luminance meter.Light source is halogen lamp.Low-pass filter (Low-pass filter) is set as 5kHz.In two sheet glass The interval (cell gap) of substrate is put into sample for 3.5 μm and in the VA element without alignment films.It is carried out using with ultraviolet light The bonding agent of hardening is by the component seal.The voltage for applying 30V on one side to the element, irradiates 78mW/cm on one side² Ultraviolet light 449 seconds (35J) of (405nm).Rugged (EYE GRAPHICS) limited liability company of rock is used in ultraviolet irradiation The more metalized lamp M04-L41 of the UV hardening of manufacture.Rectangular wave (120Hz) is applied to the element.At this point, from vertical direction pair Element irradiation light, measurement penetrate the light quantity of element.It is considered as transmitance 100% when the light quantity reaches maximum, in the light quantity To be considered as transmitance 0% when minimum.The maximum voltage of rectangular wave is set in such a way that transmitance becomes 90%.Rectangular wave Minimum voltage be set to transmitance become 0% 2.5V.Response time is to be changed to needed for 90% as transmitance from 10% (rise time time wanted；rise time；Millisecond) it indicates.

(12) elastic constant (K11: splay (splay) elastic constant, K33: bending (bend) elastic constant；At 25 DEG C Measurement；PN): the EC-1 type elastic constant manufactured when measurement using Dongyang technology (TOYO Corporation) limited liability company Analyzer.Sample is put into the vertically oriented unit that the interval (cell gap) of two panels glass substrate is 20 μm.To the list Member applies 20 volts to 0 volt of charge, measures electrostatic capacitance and applies voltage.Use " liquid-crystal apparatus handbook " (daily magazine work Retribution for sins society) formula (2.98), formula (2.101) in page 75 carry out the electrostatic capacitance (C) measured and the value for applying voltage (V) It is fitted (fitting), the value of elastic constant is obtained according to formula (2.100).

(13) specific resistance (ρ；It is measured at 25 DEG C；Ω cm): sample 1.0mL is injected in the container for having electrode.To institute It states container and applies DC voltage (10V), the DC current after measurement 10 seconds.Specific resistance is to calculate according to the following formula.(specific resistance) ={ (voltage) × (capacitor of container) }/{ (DC current) × (dielectric constant of vacuum) }.

(14) pre-tilt angle (degree): using light splitting ellipsometer M-2000U, (J.A. Wu Lamu share has in the measurement of pre-tilt angle Limit company (J.A.Woollam Co., Inc.) manufacture).

(15) orientation stability (liquid crystal aligning axis stability): the liquid crystal aligning axis of the electrode side of liquid crystal display element is evaluated Variation.Measurement applies the liquid crystal aligning angle φ ((before) before) of the electrode side before stress, thereafter, applies square to element After twenty minutes, short circuit 1 second measures the liquid crystal aligning angle φ of electrode side again after 1 second and after five minutes by shape wave 4.5V, 60Hz ((after) later).The variation of liquid crystal aligning angle after calculating according to these values and using following formula 1 second and after five minutes Δφ(deg.)。

Δ φ (deg.)=φ (after)-φ (before) (formula 2)

It covers special Bach, D. Bryant and P.J. with J. Xi Er Fick, B. Zhan Xun, the conspicuous Singh of C., J.F. Chinese mugwort Germania, E. and wins This (J.Hilfiker, B.Johs, C.Herzinger, J.F.Elman, E.Montbach, D.Bryant, and P.J.Bos), " solid film " (Thin Solid Films), 455-456, (2004) 596-600 are with reference to carrying out these measurements.It may be said that The change rate of the smaller liquid crystal aligning axis of Δ φ is smaller, and the stability of liquid crystal aligning axis is better.

[synthesis example 1]

The synthesis of compound (PC-1)

Step 1 is rapid

Trifluoromethanesulfanhydride anhydride (25.0g) and methylene chloride (80.0ml) are put into reactor, and are cooled to 0 DEG C.To Methylene chloride (160ml) solution of compound (T-1) (10.3g) and triethylamine (8.97g) is wherein slowly added dropwise.It will be obtained Solution is injected into ethylene glycol (165g), is stirred at room temperature 12 hours.Reaction mixture is injected into water, dichloromethane is utilized Alkane extracts water layer.Organic layer obtained is cleaned using water, is dried using anhydrous magnesium sulfate.It is depressurizing Under the solution is concentrated, residue is purified using silica gel chromatography (volume ratio, heptane: ethyl acetate=1:1) And obtain compound (T-2) (6.18g；44%).

Second step

By compound (T-2) (6.18g), 3,4- dihydro -2H- pyrans (3.57g), para-methylbenzenepyridinsulfonate sulfonate (Pyridiniump-toluenesulfonate, PPTS) (0.970g) and methylene chloride (60.0ml) are put into reactor, It is stirred at room temperature 12 hours.Reaction mixture is injected into water, water layer is extracted using methylene chloride.Utilize water pair Organic layer obtained is cleaned, and is dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, is utilized Silica gel chromatography (volume ratio, heptane: ethyl acetate=4:1) purifies residue and obtains compound (T-3) (9.15g； 97%).Furthermore THP indicates THP trtrahydropyranyl.

Third step

By compound (T-3) (9.15g), tetrahydrofuran (Tetrahydrofuran, THF) (45.0ml) and water (45.0ml) is put into reactor, and is cooled to 0 DEG C.Lithium hydroxide monohydrate (3.14g) is added thereto, is restored on one side It is stirred on one side to room temperature 7 hours.Reaction mixture is injected into water, slowly add 6N hydrochloric acid (15ml) and after being set as acidity, Water layer is extracted using ethyl acetate.Organic layer obtained is cleaned using water, is carried out using anhydrous magnesium sulfate It is dry.The solution is concentrated under reduced pressure and obtains compound (T-4) (5.07g；59%).

Step 4 is rapid

By according to the method recorded in International Publication No. 2014/097952 synthesize compound (T-5) (124g), three Ethamine (52.4g) and THF (3100ml) are put into reactor, and are cooled to 0 DEG C.Compound (T-6) slowly is added dropwise thereto (50.0g) is stirred 3 hours at 50 DEG C.Reaction mixture is injected into saline solution, water layer is carried out using t-butyl methyl ether Extraction.Successively organic layer obtained is cleaned using water and saline solution, is dried using anhydrous magnesium sulfate.It is depressurizing Under the solution is concentrated, residue is purified using silica gel chromatography (volume ratio, heptane: ethyl acetate=4:1) And obtain compound (T-7) (55.6g；37%).

Step 5 is rapid

By compound (T-4) (3.64g), compound (T-7) (5.00g), dimethyl aminopyridine (Dimethylaminopyridine, DMAP) (0.807g) and methylene chloride (75.0ml) are put into reactor, and are cooled to 0℃.The two of dicyclohexylcarbodiimide (Dicyclohexylcarbodiimide, DCC) (4.09g) are slowly added dropwise thereto Chloromethanes (25.0ml) solution stirs 12 hours while restoring to room temperature.By insoluble matter furnace not after, reaction mixture is infused Enter into water, water layer is extracted using methylene chloride.Organic layer obtained is cleaned using water, utilizes anhydrous sulphur Sour magnesium is dried.The solution is concentrated under reduced pressure, using silica gel chromatography (volume ratio, heptane: ethyl acetate= 5:1) residue is purified and obtains compound (T-8) (7.35g；94%).

Step 6 is rapid

Compound (T-8) (7.35g), PPTS (1.56g), THF (37.0ml) and methanol (37.0ml) are put into reaction In device, stirred 4 hours at 50 DEG C.Reaction mixture is injected into water, water layer is extracted using ethyl acetate.Utilize water Organic layer obtained is cleaned, is dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, benefit Residue is purified with silica gel chromatography (volume ratio, toluene: ethyl acetate=2:1).In turn, pass through the recrystallization from heptane It is purified, to obtain compound (PC-1) (3.54g；56%).

The NMR assay value of compound (PC-1) obtained is as described below.

¹H-NMR: chemical shift δ (ppm；CDCl₃): 6.30 (s, 1H), 6.09 (s, 1H), 5.88 (d, J=1.2Hz, 1H), 5.57(s,1H),4.35-4.26(m,2H),4.24(s,2H),4.21-4.14(m,2H),3.78-3.73(m,2H),3.62(t, J=4.7Hz, 2H), 2.27 (t, J=6.3Hz, 1H), 1.97-1.90 (m, 4H), 1.85-1.64 (m, 8H), 1.48-1.38 (m, 1H),1.34-1.18(m,6H),1.18-0.78(m,16H).

The physical property of compound (PC-1) is as described below.

Transition temperature: C 37.3I.

Compound (1-1) can be synthesized with reference to the method recorded in synthesis example to compound (1-7).

Compound in embodiment is the definition according to following Table 3, is indicated by mark.In table 3, with 1 or 4 cyclohexylidene Relevant spatial configuration is anti-configuration.Number in the parantheses after mark corresponds to the number of compound.The mark of (-) Refer to other liquid crystal compounds.The ratio (percentage) of liquid crystal compounds is the quality hundred of the quality based on liquid-crystal composition Divide rate (quality %).Finally, concluding the characteristic value of composition.

Table 3. uses the Description Method of the compound of mark

R-(A₁)-Z₁-…··-Z_n-(A_n)-R′

The embodiment of element

1. raw material

Injection is added with the liquid-crystal composition of polar compound in the element for not having alignment films.In irradiation ultraviolet light Afterwards, the vertical orientation of the liquid crystal molecule in the element is studied.Raw material is illustrated first.Raw material is composition M1 to composition M25, polar compound (PC-1) to polar compound (PC-10), polymerizable compound (RM-1) to polymerism Compound (RM-8), and sequentially enumerated.

[composition M1]

NI=73.2 DEG C；Tc<-20℃；Δ n=0.113；Δ ε=- 4.0；Vth=2.18V；η=22.6mPas.

[composition M2]

NI=82.8 DEG C；Tc<-30℃；Δ n=0.118；Δ ε=- 4.4；Vth=2.13V；η=22.5mPas.

[composition M3]

NI=78.1 DEG C；Tc<-30℃；Δ n=0.107；Δ ε=- 3.2；Vth=2.02V；η=15.9mPas.

[composition M4]

NI=88.5 DEG C；Tc<-30℃；Δ n=0.108；Δ ε=- 3.8；Vth=2.25V；η=24.6mPas； VHR-1=99.1%；VHR-2=98.2%；VHR-3=97.8%.

[composition M5]

NI=81.1 DEG C；Tc<-30℃；Δ n=0.119；Δ ε=- 4.5；Vth=1.69V；η=31.4mPas.

[composition M6]

NI=98.8 DEG C；Tc<-30℃；Δ n=0.111；Δ ε=- 3.2；Vth=2.47V；η=23.9mPas.

[composition M7]

NI=77.5 DEG C；Tc<-30℃；Δ n=0.084；Δ ε=- 2.6；Vth=2.43V；η=22.8mPas.

[composition M8]

NI=70.6 DEG C；Tc<-20℃；Δ n=0.129；Δ ε=- 4.3；Vth=1.69V；η=27.0mPas.

[composition M9]

NI=93.0 DEG C；Tc<-30℃；Δ n=0.123；Δ ε=- 4.0；Vth=2.27V；η=29.6mPas.

[composition M10]

NI=87.6 DEG C；Tc<-30℃；Δ n=0.126；Δ ε=- 4.5；Vth=2.21V；η=25.3mPas.

[composition M11]

NI=93.0 DEG C；Tc<-20℃；Δ n=0.124；Δ ε=- 4.5；Vth=2.22V；η=25.0mPas.

[composition M12]

NI=76.4 DEG C；Tc<-30℃；Δ n=0.104；Δ ε=- 3.2；Vth=2.06V；η=15.6mPas.

[composition M13]

NI=78.3 DEG C；Tc<-20℃；Δ n=0.103；Δ ε=- 3.2；Vth=2.17V；η=17.7mPas.

[composition M14]

NI=81.2 DEG C；Tc<-20℃；Δ n=0.107；Δ ε=- 3.2；Vth=2.11V；η=15.5mPas.

[composition M15]

NI=88.7 DEG C；Tc<-30℃；Δ n=0.115；Δ ε=- 1.9；Vth=2.82V；η=17.3mPas.

[composition M16]

NI=89.9 DEG C；Tc<-20℃；Δ n=0.122；Δ ε=- 4.2；Vth=2.16V；η=23.4mPas.

[composition M17]

NI=77.1 DEG C；Tc<-20℃；Δ n=0.101；Δ ε=- 3.0；Vth=2.04V；η=13.9mPas.

[composition M18]

NI=75.9 DEG C；Tc<-20℃；Δ n=0.114；Δ ε=- 3.9；Vth=2.20V；η=24.7mPas.

[composition M19]

NI=75.9 DEG C；Δ n=0.101；Δ ε=- 2.7.

[composition M20]

NI=78.4 DEG C；Tc<-30℃；Δ n=0.105；Δ ε=- 2.7；Vth=2.43V；η=16.2mPas.

[composition M21]

NI=76.0 DEG C；Tc<-20℃；Δ n=0.097；Δ ε=- 3.0；Vth=2.20V.

[composition M22]

NI=75.3 DEG C；Δ n=0.109；Δ ε=- 3.1；Vth=2.29V.

[composition M23]

NI=73.5 DEG C；Tc<-20℃；Δ n=0.100；Δ ε=- 2.6.

[composition M24]

NI=74.8 DEG C；Tc<-20℃；Δ n=0.099；Δ ε=- 3.2.

[composition M25]

NI=71.1 DEG C；Tc<-20℃；Δ n=0.105；Δ ε=- 2.7.

[composition M26]

NI=75.6 DEG C；Δ n=0.104；Δ ε=- 2.4.

[composition M27]

NI=76.5 DEG C；Tc<-20℃；Δ n=0.098；Δ ε=- 3.0；Vth=2.15V；η=16.2mPas.

[composition M28]

NI=75.3 DEG C；Tc<-20℃；Δ n=0.102；Δ ε=- 2.6；Vth=2.41V；η=17.5mPas.

Polar compound below (PC-1) to polar compound (PC-7) is used as the first additive, by polar compound (PC-8) to polar compound (PC-10) is used as third additive.

Polymerizable compound below (RM-1) to polymerizable compound (RM-8) is used as the second additive.

2. the orientation of liquid crystal display element

[embodiment 1]

Composition (M1) will be made an addition to the ratio of 1.5 mass % as the polar compound of the first additive (PC-1) In.Liquid-crystal composition of the invention added with the polar compound is enclosed to the VA for the glass substrate for not having alignment films In element, and vertical orientation of the composition on substrate is confirmed, as the result is shown vertical orientation out.

[comparative example 1]

As a comparison, element is made using only composition (M1) and using method same as Example 1, and to substrate On vertical orientation confirmed, as a result do not show vertical orientation.

[embodiment 2 to embodiment 32]

Change composition type and polar compound concentration come prepare addition polar compound liquid-crystal composition, and Vertical orientation is confirmed using method same as Example 1.By composition expression the case where having carried out orientation on substrate For "○", will be without being orientated the case where, is expressed as "×".Result is summarized in table 4.

According to the result of table 4, in the element using the liquid-crystal composition added with the first additive, vertical orientation is shown Property.On the other hand, in the element using the liquid-crystal composition for being not added with the first additive, vertical orientation is not shown.The knot Fruit shows the first additive of the invention with the vertical orientation in liquid crystal display element.

3. the dissolubility of polar compound

[embodiment 33 to embodiment 35 and comparative example 2 to comparative example 4]

Polar compound (PC-1) to polar compound (PC-3) is made an addition into composition with the ratio of 3.0 mass % (M27) and in composition (M28), to obtain liquid-crystal composition of the invention.Freezing by the liquid-crystal composition at -20 DEG C A week is saved in library, the case where crystallizing will be precipitated from the liquid-crystal composition and is expressed as "○", the case where crystallizing will be precipitated It is expressed as "×".As a comparison, for the polar compound (PC-8) being only added to as third additive to polar compound (PC-10) liquid-crystal composition observes the presence or absence of crystallization precipitation using identical method.Result is summarized in table 5.

The dissolubility of 5. polar compound of table

Example	Composition	First additive	Quality %	Third additive	Quality %	Dissolubility	Δε	Tni
									Embodiment 33	M27	PC-1	3.0	-	-	○	-3	72
Embodiment 34	M28	PC-2	3.0	-	-	○	-2.6	70.8
									Embodiment 35	M28	PC-3	3.0	-	-	○	-2.6	72.3
Comparative example 2	M27	-	-	PC-8	3.0	×	-2.8	72.9
									Comparative example 3	M28	-	-	PC-9	3.0	×	-2.4	72.1
Comparative example 4	M28	-	-	PC-10	3.0	×	-2.4	74.1

According to table 5: in the liquid-crystal composition of embodiment 33 to embodiment 35, though change composition or polarity The type of object is closed, but crystallization is not precipitated.The result shows the favorable solubility of polar compound of the invention.On the other hand, Crystallization has been precipitated into the liquid-crystal composition of comparative example 4 in comparative example 2.The result shows only addition as third additive When polar compound, dissolubility is bad.In turn, the orientation to the liquid-crystal composition in liquid crystal display element carries out true Recognize, as a result: compared with comparative example 2 to comparative example 4, the liquid-crystal composition of embodiment 33 to embodiment 35 shows good orientation Property.

According to the result: being imported with-O (CH in the end of polar group₂)_nOH base and branch in molecular end Polar compound with polymerism base and polar group in structure has the good vertical orientation in liquid crystal display element, into And with the good dissolubility to liquid-crystal composition, that is, nematic low lower limit temperature under low temperature.

[industrial availability]

Liquid-crystal composition of the invention can control the orientation of liquid crystal molecule in the element for not having alignment films.Containing The liquid crystal display element of composition is stated with the response time is short, voltage retention is big, starting voltage is low, contrast is than big, the service life is long Etc. characteristics, therefore can be used for liquid crystal projection apparatus, LCD TV etc..

Claims

1. a kind of liquid-crystal composition, it is characterised in that: contain in the polar compound for being selected from polymerism represented by formula (1) extremely A kind of few compound has nematic phase and negative dielectric anisotropy as the first additive,

In formula (1),

R¹For hydrogen or the alkyl of carbon number 1 to 15, in the alkyl, at least one-CH₂It can replace through-O- or-S-, at least one- CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；Ring A¹And ring A²For 1,2- cyclopropylidene, the Asia 1,3- cyclobutyl, 1,3- cyclopentylene, 1,4- cyclohexylidene, 1,4- cycloheptylidene, the Asia 1,4- cyclohexene Base, 1,4- phenylene, naphthalene -2,6- diyl, decahydronaphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl, oxinane -2, 5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, in these rings, at least one hydrogen can Alkenyloxy group through fluorine, chlorine, the alkyl of carbon number 1 to 10, the alkenyl of carbon number 2 to 10, the alkoxy of carbon number 1 to 10 or carbon number 2 to 10 Replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；A is 0,1,2,3 or 4；Z¹For singly-bound or the alkylene of carbon number 1 to 6 Base, in the alkylidene, at least one-CH₂It can replace through-O- ,-CO- ,-COO- ,-OCO- or-OCOO-, at least one- CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；Sp¹、Sp²、Sp³And Sp⁴For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,-COO- ,- OCO- or-OCOO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen It can replace through fluorine or chlorine；Sp⁵For the alkylidene of carbon number 2 to 10, in the alkylidene, at least one-CH₂It can replace through-O-； M¹、M²、M³And M⁴For the alkane for the carbon number 1 to 5 that hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine Base；R²For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, In these bases, at least one hydrogen can replace through fluorine or chlorine；X¹For-OH ,-NH₂、-OR³、-N(R³)₂,-COOH ,-SH or-Si (R³)₃, herein, R³For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, at least one-CH₂It can replace through-O-, at least one A-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine.

2. liquid-crystal composition according to claim 1, it is characterised in that: containing represented to formula (1-7) selected from formula (1-1) At least one of the polar compound of polymerism compound as the first additive,

Formula (1-1) is into formula (1-7), R¹For the alkyl of carbon number 1 to 10；Y¹、Y²、Y³、Y⁴、Y⁵And Y⁶For hydrogen, fluorine, methyl or ethyl； Sp¹And Sp⁴For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least One hydrogen can replace through fluorine or chlorine；R²For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂CH₂It can be through-CH =CH- or-C ≡ C- replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine.

3. liquid-crystal composition according to claim 1, it is characterised in that: the ratio of the first additive be 10 mass % with Under.

4. liquid-crystal composition according to claim 1, it is characterised in that: contain and be selected from compound represented by formula (2) At least one compound as first composition,

In formula (2), R⁴And R⁵For hydrogen, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, carbon number 2 The alkyl of the carbon number 1 to 12 replaced to 12 alkenyloxy group or at least one hydrogen through fluorine or chlorine；Ring B and ring D is the Asia 1,4- hexamethylene The 1,4- that base, 1,4- cyclohexadienylidene, oxinane -2,5- diyl, 1,4- phenylene, at least one hydrogen replace through fluorine or chlorine is sub- Naphthalene -2,6- diyl that phenyl, naphthalene -2,6- diyl, at least one hydrogen replace through fluorine or chlorine, chromogen alkane -2,6- diyl or at least Chromogen alkane -2,6- the diyl that one hydrogen replaces through fluorine or chlorine；Ring C is the fluoro- 1,4- phenylene of 2,3- bis-, the fluoro- Asia 1,4- the chloro- 3- of 2- Phenyl, the fluoro- 5- methyl-1 of 2,3- bis-, 4- phenylene, tri- fluoronaphthalene -2,6- diyl of 3,4,5-, 7,8- difluoro chromogen alkane -2,6- two Base, 3,4,5,6- tetrafluoro fluorenes -2,7- diyl, 4,6- difluorodiphenyl and furans -3,7- diyl, 4,6- difluorodiphenyl bithiophene -3, 7- diyl or 1,1,6,7- tetrafluoro indane -2,5- diyl；Z²And Z³For singly-bound, ethylidene, ethenylidene, methylene oxygroup or carbonyl oxygen Base；B be 0,1,2 or 3, c be 0 or 1, and b and c's and be 3 or less.

5. liquid-crystal composition according to claim 1, it is characterised in that: containing selected from formula (2-1) to formula (2-35) institute table At least one of compound shown compound as first composition,

6. liquid-crystal composition according to claim 4, it is characterised in that: the ratio of first composition is 10 mass % to 90 matter Measure the range of %.

7. liquid-crystal composition according to claim 1, it is characterised in that: contain and be selected from compound represented by formula (3) At least one compound as second composition,

In formula (3), R⁶And R⁷For the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 alkenyl, at least one The alkenyl for the carbon number 2 to 12 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that hydrogen replaces through fluorine or chlorine replace through fluorine or chlorine； Ring E and ring F is 1,4- cyclohexylidene, 1,4- phenylene, the fluoro- 1,4- phenylene of 2- or the fluoro- 1,4- phenylene of 2,5- bis-；Z⁴For list Key, ethylidene, ethenylidene, methylene oxygroup or carbonyloxy group；D is 1,2 or 3.

8. liquid-crystal composition according to claim 1, it is characterised in that: containing selected from formula (3-1) to formula (3-13) institute table At least one of compound shown compound as second composition,

Formula (3-1) is into formula (3-13), R⁶And R⁷For the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 The carbon number that the alkyl or at least one hydrogen for the carbon number 1 to 12 that alkenyl, at least one hydrogen replace through fluorine or chlorine replace through fluorine or chlorine 2 to 12 alkenyl.

9. liquid-crystal composition according to claim 7, it is characterised in that: the ratio of second composition is 10 mass % to 90 matter Measure the range of %.

10. liquid-crystal composition according to claim 4, it is characterised in that: contain and be selected from compound represented by formula (3) At least one compound as second composition,

11. liquid-crystal composition according to claim 1, it is characterised in that: contain and be selected from polymerism represented by formula (4) At least one of object compound is closed as the second additive,

In formula (4), ring G and ring J are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalene, 2- naphthalene, oxinane -2- base, 1,3- bis- Oxane -2- base, pyrimidine -2-base or pyridine -2- base, in these rings, at least one hydrogen can through fluorine, chlorine, carbon number 1 to 12 alkyl, The alkyl for the carbon number 1 to 12 that the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces；Ring I is 1,4- sub- Cyclohexyl, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -1,2- diyl, naphthalene -1,3- diyl, naphthalene -1,4- diyl, naphthalene -1,5- Diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- diyl, naphthalene -2,3- diyl, naphthalene -2,6- diyl, naphthalene -2,7- diyl, Oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, in these rings, At least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one hydrogen through fluorine or chlorine The alkyl of substituted carbon number 1 to 12 replaces；Z⁵And Z⁶For singly-bound or the alkylidene of carbon number 1 to 10, the Z⁵And Z⁶In, at least one A-CH₂It can replace through-O- ,-CO- ,-COO- or-OCO-, and at least one-CH₂CH₂It can be through-CH=CH- ,-C (CH₃) =CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, at least one hydrogen can replace through fluorine or chlorine；P¹、P²And P³It is poly- Conjunction property base；Sp⁶、Sp⁷And Sp⁸For singly-bound or the alkylidene of carbon number 1 to 10, the Sp⁶、Sp⁷And Sp⁸In, at least one-CH₂It can Replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, until Few hydrogen can replace through fluorine or chlorine；H is 0,1 or 2；E, f and g be 0,1,2,3 or 4, and e, f and g and be 1 or more.

12. liquid-crystal composition according to claim 11, it is characterised in that: in formula (4), P¹、P²And P³For selected from formula (P- 1) base into polymerism base represented by formula (P-5),

Formula (P-1) is into formula (P-5), M⁵、M⁶And M⁷It is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine or chlorine The alkyl of substituted carbon number 1 to 5.

13. liquid-crystal composition according to claim 1, it is characterised in that: containing selected from formula (4-1) to formula (4-29) institute table At least one of polymerizable compound shown compound as the second additive,

Formula (4-1) is into formula (4-29), P¹、P²And P³For the base in the polymerism base represented by the formula (P-1) to formula (P-3)； Sp⁶、Sp⁷And Sp⁸For singly-bound or the alkylidene of carbon number 1 to 10, the Sp⁶、Sp⁷And Sp⁸In, at least one-CH₂Can through-O- ,- COO- ,-OCO- or-OCOO- replace, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, at least one hydrogen It can replace through fluorine or chlorine；

Formula (P-1) is into formula (P-3), M⁵、M⁶And M⁷It is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine or chlorine The alkyl of substituted carbon number 1 to 5.

14. liquid-crystal composition according to claim 11, it is characterised in that: the ratio of the second additive is 0.03 mass % To the range of 10 mass %.

15. liquid-crystal composition according to claim 4, it is characterised in that: contain and be selected from polymerism represented by formula (4) At least one of object compound is closed as the second additive,

16. liquid-crystal composition according to claim 7, it is characterised in that: contain and be selected from polymerism represented by formula (4) At least one of object compound is closed as the second additive,

17. liquid-crystal composition according to claim 10, it is characterised in that: contain and be selected from polymerism represented by formula (4) At least one of compound compound as the second additive,

18. liquid-crystal composition according to claim 1, it is characterised in that: containing selected from formula (5-1) and formula (5-2) institute table At least one of polar compound of polymerism shown compound as third additive,

In formula (5-1) and formula (5-2), R⁵⁰For hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to The fluorine-substituted carbon number of the alkyl or at least one hydrogen for the carbon number 1 to 12 that 12 alkenyl, at least one hydrogen replace through fluorine or chlorine 2 to 12 alkenyl；R⁵¹For-OH ,-NH₂、-OR⁵³、-N(R⁵³)₂,-COOH ,-SH or-Si (R⁵³)₃Represented base, herein, R⁵³ For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂It can replace through-O-, at least one-CH₂CH₂Can through- CH=CH- replaces, and in these bases, at least one hydrogen can be fluorine-substituted；Ring A⁵⁰And ring B⁵⁰For 1,4- cyclohexylidene, the Asia 1,4- ring Hexenyl, 1,4- phenylene, naphthalene -2,6- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- Diyl or pyridine -2,5- diyl, in these rings, at least one hydrogen can through fluorine, the alkyl of carbon number 1 to 12, carbon number 1 to 12 alcoxyl The alkyl of base or the fluorine-substituted carbon number 1 to 12 of at least one hydrogen replaces；Z⁵⁰For singly-bound ,-CH₂CH₂,-CH=CH- ,-C ≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂Or-CF=CF-；Sp⁵¹、Sp⁵³And Sp⁵⁴For singly-bound or carbon The alkylidene of number 1 to 7, in the alkylidene, at least one-CH₂It can replace through-O- ,-COO- or-OCO-, at least one- CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be fluorine-substituted；Sp⁵²For the Asia of singly-bound or carbon number 1 to 7 Alkyl, in the alkylidene, at least one-CH₂It can replace through-COO- or-OCO-, at least one-CH₂CH₂It can be through-CH= CH- replaces, and in these bases, at least one hydrogen can be fluorine-substituted；a⁵⁰It is 0,1,2,3 or 4.

19. a kind of liquid crystal display element, it is characterised in that: contain liquid-crystal composition as described in claim 1.

20. a kind of liquid crystal display element without alignment films, it is characterised in that: contain liquid crystal group as described in claim 1 Object is closed, and the polymerizable compound in the liquid-crystal composition is polymerize.